Detergent compostions inhibiting dye transfer comprising copolymers of n-vinylimidazole and n-vinylpyrrolidone

ABSTRACT

A detergent composition comprises clay, a surfactant system and a copolymer of N-vinylimidazole and N-vinylpyrrolidone. The copolymer is present in the detergent composition in an amount of 0.01% to 10.0% by weight. The copolymer has an average molecular weight of from 5,000 to 50,000 and a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of from 1:1 to 1:02.

FIELD OF THE INVENTION

The present invention relates to a composition and a process forinhibiting dye transfer between fabrics during washing. More inparticular, the present invention relates to detergent compositionscomprising N-vinylimidazole N-vinylpyrrolidone copolymers having lowaverage molecular weight

BACKGROUND OF THE INVENTION

One of the most persistent and troublesome problems arising duringmodern fabric laundering operations is the tendency of some coloredfabrics to release dye into the laundering solutions. The dye is thentransferred onto other fabrics being washed therewith.

One way of overcoming this problem would be to complex or adsorb thefugitive dyes washed out of dyed fabrics before they have theopportunity to become attached to other articles in the wash.

Polymers have been used within detergent compositions to inhibit dyetransfer.

One type of such polymers are N-vinylimidazole homo- and copolymers.Examples of said polymers are described in DE 2 814 287-A relates todetergent compositions comprising 0.1 to 10 wt % water-soluble orwater-dispersible N-vinyl imidazole homo- or copolymer in combinationwith anionic and/or nonionic surfactants and other detergentingredients. EP 372 291 relates to a process for washingdiscolouration-sensitive textiles. The wash liquor containsanionic/nonionic surfactants and watersoluble polymers e.g. (co)polymersN-vinylimidazole, N-vinyloxazolidone or N-vinylpyrrolidone. EP 327 927describes a granular detergent additive comprising water-solublepolymeric compounds based on N-vinylpyrrolidone and/or N-vinylimidazoleand/or N-vinyloxazolidone and cationic compounds. DE 4027832-A assignedto Henkel discloses electrolyte-free liquid detergent compositionscomprising zeolite A, nonionic surfactants and dye transfer inhibitingpolymers. The dye transfer inhibiting polymers are homo- and copolymersselected from N-vinylpyrrolidone and/or N-vinylimidazole and/orN-vinyloxazolidone.

These prior art documents describe N-vinyl imidazole copolymers as dyetransfer inhibiting polymers having a molecular weight range from 10,000to 1,000,000. The preferred N-vinylimidazole copolymers that aredescribed have a molecular weight from 20,000 to 200,000.

Unfortunately, the overall detergency performance of detergentcompositions formulated with said N-vinylimidazole copolymers areaffected by the presence of said polymers. As a consequence, thedetergent formulator is faced with a difficult task of providingdetergent compositions which have an excellent overall detergentperformance.

It has now been found that a selected group of N-vinylimidazolecopolymers are very efficient in eliminating transfer of solubilized orsuspended dyes while not adversely affecting the overall detergencyperformance of the detergent composition formulated therewith.

This finding allows to formulate detergent compositions which exhibitexcellent cleaning and dye transfer inhibiting properties.

According to another embodiment of this invention a process is alsoprovided for laundering operations involving colored fabrics.

SUMMARY OF THE INVENTION

The present invention relates to detergent compositions comprising apolymer selected from N-vinylimidazole N-vinylpyrrolidone copolymerscharacterized in that said polymer has an average molecular weight rangefrom 5,000 to 50,000.

DETAILED DESCRIPTION OF THE INVENTION

The N-vinylimidazole N-vinylpyrrolidone copolymer

The present invention relates to detergent compositions comprising apolymer selected from N-vinylimidazole N-vinylpyrrolidone copolymerscharacterized in that said polymer has an average molecular weight rangefrom 5,000 to 50,000 more preferably from 8,000 to 30,000, mostpreferably from 10,000 to 20,000.

It has been surprisingly found that an excellent overall detergencyperformance of detergent compositions comprising said copolymers can beobtained by selecting a specific average molecular weight range from5,000 to 50,000; more preferably from 8,000 to 30,000; most preferablyfrom 10,000 to 20,000. The average molecular weight range was determinedby light scattering as described in Barth H. G. and Mays J. W. ChemicalAnalysis Vol 113. "Modern Methods of Polymer Characterization.

The N-vinylimidazole N-vinylpyrrolidone copolymers characterized byhaving said average molecular weight range provide excellent dyetransfer inhibiting properties while not adversely affecting thecleaning performance of detergent compositions formulated therewith.

In addition, it has been found that the detergency performance ofcertain detergent ingredients has been enhanced by the presence of saidN-vinylimidazole N-vinylpyrrolidone copolymers of the present invention.

The N-vinylimidazole N-vinylpyrrolidone copolymer of the presentinvention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidonefrom 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6to 0.4.

The N-vinylimidazole N-vinylpyrrolidone copolymers can be linear orbranched. The level of the N-vinylimidazole N-vinylpyrrolidone presentin the detergent compositions is from 0.01 to 10%, more preferably from0.05 to 5%, most preferably from 0.1 to 1% by weight of the detergentcomposition.

DETERGENT INGREDIENTS

The compositions according to the present invention comprise in additionto the N-vinylimidazole N-vinylpyrrolidone copolymers a surfactantsystem wherein the surfactant can be selected from nonionic and/oranionic and/or cationic and/or ampholytic and/or zwitterionic and/orsemi-polar surfactants. Preferred surfactant systems to be usedaccording to the present invention comprise as a surfactant one or moreof the nonionic surfactants described herein. These nonionic surfactantshave found to be very useful in that the dye transfer inhibitingperformance of the N-vinylimidazole N-vinylpyrrolidone copolymers hasbeen increased in the presence of said surfactants.

Nonionics

Polyethylene, polypropylene, and polybutylene oxide condensates of alkylphenols are suitable for use as the nonionic surfactant of thesurfactant systems of the present invention, with the polyethylene oxidecondensates being preferred. These compounds include the condensationproducts of alkyl phenols having an alkyl group containing from about 6to about 14 carbon atoms, preferably from about 8 to about 14 carbonatoms, in either a straight-chain or branched-chain configuration withthe alkylene oxide. In a preferred embodiment, the ethylene oxide ispresent in an amount equal to from about 2 to about 25 moles, morepreferably from about 3 to about 15 moles, of ethylene oxide per mole ofalkyl phenol. Commercially available nonionic surfactants of this typeinclude Igepal™ CO-630, marketed by the GAF Corporation; and Triton™X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company.These surfactants are commonly referred to as alkylphenol alkoxylates(e.g., alkyl phenol ethoxylates).

The condensation products of primary and secondary aliphatic alcoholswith from about 1 to about 25 moles of ethylene oxide are suitable foruse as the nonionic surfactant of the nonionic surfactant systems of thepresent invention. The alkyl chain of the aliphatic alcohol can eitherbe straight or branched, primary or secondary, and generally containsfrom about 8 to about 22 carbon atoms. Preferred are the condensationproducts of alcohols having an alkyl group containing from about 8 toabout 20 carbon atoms, more preferably from about 10 to about 18 carbonatoms, with from about 2 to about 10 moles of ethylene oxide per mole ofalcohol. Examples of commercially available nonionic surfactants of thistype include Tergitol™ 15-S-9 (the condensation product of C₁₁ -C₁₅linear alcohol with 9 moles ethylene oxide), Tergitol™ 24-L-6 NMW (thecondensation product of C₁₂ -C₁₄ primary alcohol with 6 moles ethyleneoxide with a narrow molecular weight distribution), both marketed byUnion Carbide Corporation; Neodol™ 45-9 (the condensation product of C₁₄-C₁₅ linear alcohol with 9 moles of ethylene oxide), Neodol™ 23-6.5 (thecondensation product of C₁₂ -C₁₃ linear alcohol with 6.5 moles ofethylene oxide), Neodol™ 45-7 (the condensation product of C₁₄ -C₁₅linear alcohol with 7 moles of ethylene oxide), Neodol™ 45-4 (thecondensation product of C₁₄ -C₁₅ linear alcohol with 4 moles of ethyleneoxide) marketed by Shell Chemical Company, and Kyro™ EOB (thecondensation product of C₁₃ -C₁₅ alcohol with 9 moles ethylene oxide),marketed by The Procter & Gamble Company.

Also useful as the nonionic surfactant of the surfactant systems of thepresent invention are the alkylpolysaccharides disclosed in U.S. Pat.No. 4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic groupcontaining from about 6 to about 30 carbon atoms, preferably from about10 to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside,hydrophilic group containing from about 1.3 to about 10, preferably fromabout 1.3 to about 3, most preferably from about 1.3 to about 2.7saccharide units. Any reducing saccharide containing 5 or 6 carbon atomscan be used, e.g., glucose, galactose and galactosyl moieties can besubstituted for the glucosyl moieties (optionally the hydrophobic groupis attached at the 2-, 3-, 4-, etc. positions thus giving a glucose orgalactose as opposed to a glucoside or galactoside). The intersaccharidebonds can be, e.g., between the one position of the additionalsaccharide units and the 2-, 3-, 4-, and/or 6- positions on thepreceding saccharide units.

The preferred alkylpolyglycosides have the formula

    R.sup.2 O(C.sub.n H.sub.2n O).sub.t (glyocosyl).sub.x

wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from about 10 to about 18, preferably from about 12to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 toabout 10, preferably 0; and x is from about 1.3 to about 10, preferablyfrom about 1.3 to about 3, most preferably from about 1.3 to about 2.7.The glycosyl is preferably derived from glucose. To prepare thesecompounds, the alcohol or alkylpolyethoxy alcohol is formed first andthen reacted with glucose, or a source of glucose, to form the glucoside(attachment at the 1-position). The additional glycosyl units can thenbe attached between their 1-position and the preceding glycosyl units2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.

Other suitable nonionic surfactants are the condensation products ofethylene oxide with a hydrophobic base formed by the condensation ofpropylene oxide with propylene glycol are also suitable for use as theadditional nonionic surfactant of the nonionic surfactant systems of thepresent invention. The hydrophobic portion of these compounds willpreferably have a molecular weight of from about 1500 to about 1800 andwill exhibit water insolubility. The addition of polyoxyethylenemoieties to this hydrophobic portion tends to increase the watersolubility of the molecule as a whole, and the liquid character of theproduct is retained up to the point where the polyoxyethylene content isabout 50% of the total weight of the condensation product, whichcorresponds to condensation with up to about 40 moles of ethylene oxide.Examples of compounds of this type include certain of thecommercially-available Pluronic™ surfactants, marketed by BASF.

Also suitable for use as the nonionic surfactant of the nonionicsurfactant system of the present invention, are the condensationproducts of ethylene oxide with the product resulting from the reactionof propylene oxide and ethylenediamine. The hydrophobic moiety of theseproducts consists of the reaction product of ethylenediamine and excesspropylene oxide, and generally has a molecular weight of from about 2500to about 3000. This hydrophobic moiety is condensed with ethylene oxideto the extent that the condensation product contains from about 40% toabout 80% by weight of polyoxyethylene and has a molecular weight offrom about 5,000 to about 11,000. Examples of this type of nonionicsurfactant include certain of the commercially available Tetronic™compounds, marketed by BASF.

Preferred for use as the nonionic surfactant of the surfactant systemsof the present invention are polyethylene oxide condensates of alkylphenols, condensation products of primary and secondary aliphaticalcohols with from about 1 to about 25 moles of ethylene oxide,alkylpolysaccharides, and mixtures thereof. Most preferred are C₈ -C₁₄alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and C₈ -C₁₈alcohol ethoxylates (preferably C₁₀ avg.) having from 2 to 10 ethoxygroups, and mixtures thereof.

Highly preferred nonionic surfactants are polyhydroxy fatty acid amidesurfactants of the formula: ##STR1## wherein R¹ is H, or R¹ is C₁₋₄hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R²is C₅₋₃₁ hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linearhydrocarbyl chain with at least 3 hydroxyls directly connected to thechain, or an alkoxylated derivative thereof. Preferably, R¹ is methyl,R² is a straight C₁₁₋₁₅ alkyl or alkenyl chain such as coconut alkyl ormixtures thereof, and Z is derived from a reducing sugar such asglucose, fructose, maltose, lactose, in a reductive amination reaction.

When included in such laundry detergent compositions, the nonionicsurfactant systems of the present invention act to improve thegreasy/oily stain removal properties of such laundry detergentcompositions across a broad range of laundry conditions.

Anionic Surfactants

Highly preferred anionic surfactants include alkyl alkoxylated sulfatesurfactants which can be water soluble salts or acids of the formulaRO(A)_(m) SO3M wherein R is an unsubstituted C₁₀ -C₂₄ alkyl orhydroxyalkyl group having a C₁₀ -C₂₄ alkyl component, preferably a C₁₂-C₂₀ alkyl or hydroxyalkyl, more preferably C₁₂ -C₁₈ alkyl orhydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero,typically between about 0.5 and about 6, more preferably between about0.5 and about 3, and M is H or a cation which can be, for example, ametal cation (e.g., sodium, potassium, lithium, calcium, magnesium,etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylatedsulfates as well as alkyl propoxylated sulfates are contemplated herein.Specific examples of substituted ammonium cations include methyl-,dimethyl, trimethyl-ammonium cations and quaternary ammonium cationssuch as tetramethyl-ammonium and dimethyl piperdinium cations and thosederived from alkylamines such as ethylamine, diethylamine,triethylamine, mixtures thereof, and the like. Exemplary surfactants areC₁₂ -C₁₈ alkyl polyethoxylate (1.0) sulfate (C₁₂ -C₁₈ E(1.0)M), C₁₂ -C₁₈alkyl polyethoxylate (2.25) sulfate (C₁₂ -C₁₈ E(2.25)M), C₁₂ -C₁₈ alkylpolyethoxylate (3.0) sulfate (C₁₂ -C₁₈ E(3.0)M), and C₁₂ -C₁₈ alkylpolyethoxylate (4.0) sulfate (C₁₂ -C₁₈ E(4.0)M), wherein M isconveniently selected from sodium and potassium.

Suitable anionic surfactants to be used are alkyl ester sulfonatesurfactants including linear esters of C₈ -C₂₀ carboxylic acids (i.e.,fatty acids) which are sulfonated with gaseous SO₃ according to "TheJournal of the American Oil Chemists Society", 52 (1975), pp. 323-329.Suitable starting materials would include natural fatty substances asderived from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundryapplications, comprise alkyl ester sulfonate surfactants of thestructural formula: ##STR2## wherein R³ is a C₈ -C₂₀ hydrocarbyl,preferably an alkyl, or combination thereof, R⁴ is a C₁ -C₆ hydrocarbyl,preferably an alkyl, or combination thereof, and M is a cation whichforms a water soluble salt with the alkyl ester sulfonate. Suitablesalt-forming cations include metals such as sodium, potassium, andlithium, and substituted or unsubstituted ammonium cations, such asmonoethanolamine, diethanolamine, and triethanolamine. Preferably, R³ isC₁₀ -C₁₆ alkyl, and R⁴ is methyl, ethyl or isopropyl. Especiallypreferred are the methyl ester sulfonates wherein R³ is C₁₀ -C₁₆ alkyl.

Other suitable anionic surfactants include the alkyl sulfate surfactantswhich can be water soluble salts or acids of the formula ROSO₃ M whereinR preferably is a C₁₀ -C₂₄ hydrocarbyl, preferably an alkyl orhydroxyalkyl having a C₁₀ -C₂₀ alkyl component, more preferably a C₁₂-C₁₈ alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkalimetal cation (e.g. sodium, potassium, lithium), or ammonium orsubstituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammoniumcations and quaternary ammonium cations such as tetramethyl-ammonium anddimethyl piperdinium cations and quaternary ammonium cations derivedfrom alkylamines such as ethylamine, diethylamine, triethylamine, andmixtures thereof, and the like). Typically, alkyl chains of C₁₂ -C₁₆ arepreferred for lower wash temperatures (e.g. below about 50° C.) andC₁₆₋₁₈ alkyl chains are preferred for higher wash temperatures (e.g.above about 50° C.).

Other anionic surfactants useful for detersive purposes can also beincluded in the laundry detergent compositions of the present invention.These can include salts (including, for example, sodium, potassium,ammonium, and substituted ammonium salts such as mono-, di- andtriethanolamine salts) of soap, C₉ -C₂₀ linear alkylbenzenesulfonates,C₈ -C₂₂ primary or secondary alkanesulfonates, C₈ -C₂₄ olefinsulfonates,sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzedproduct of alkaline earth metal citrates, e.g., as described in Britishpatent specification No. 1,082,179, C₈ -C₂₄ alkylpolyglycolethersulfates(containing up to 10 moles of ethylene oxide); alkyl glycerolsulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerolsulfates, alkyl phenol ethylene oxide ether sulfates, paraffinsulfonates, alkyl phosphates, isethionates such as the acylisethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates,monoesters of sulfosuccinates (especially saturated and unsaturated C₁₂-C₁₈ monoesters) and diesters of sulfosuccinates (especially saturatedand unsaturated C₆ -C₁₂ diesters), acyl sarcosinates, sulfates ofalkylpolysaccharides such as the sulfates of alkylpolyglucoside (thenonionic nonsulfated compounds being described below), branched primaryalkyl sulfates, and alkyl polyethoxy carboxylates such as those of theformula RO(CH₂ CH₂ O)_(k) --CH₂ COO--M+ wherein R is a C₈ -C₂₂ alkyl, kis an integer from 0 to 10, and M is a soluble salt-forming cation.Resin acids and hydrogenated resin acids are also suitable, such asrosin, hydrogenated rosin, and resin acids and hydrogenated resin acidspresent in or derived from tall oil. Further examples are described in"Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perryand Berch). A variety of such surfactants are also generally disclosedin U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al. atColumn 23, line 58 through Column 29, line 23 (herein incorporated byreference).

When included therein, the laundry detergent compositions of the presentinvention typically comprise from about 1% to about 40%, preferably fromabout 3% to about 20% by weight of such anionic surfactants.

The alkyl alkoxylated sulfate surfactants are preferred over the alkylsulfates and alkyl benzene sulfonates in that these alkyl alkoxylatedsulfate surfactants synergistically improve the dye transfer inhibitingperformance of the N-vinyl imidazole N-vinylpyrrolidone copolymers.

The laundry detergent compositions of the present invention may alsocontain cationic, ampholytic, zwitterionic, and semi-polar surfactants,as well as nonionic surfactants other than those already describedherein. Preferred cationic surfactant systems include nonionic andampholytic surfactants.

Cationic detersive surfactants suitable for use in the laundry detergentcompositions of the present invention are those having one long-chainhydrocarbyl group. Examples of such cationic surfactants include theammonium surfactants such as alkyldimethylammonium halogenides, andthose surfactants having the formula:

     R.sup.2 (OR.sup.3).sub.y ! R.sup.4 (OR.sup.3).sub.y !.sub.2 R.sup.5 N+X--

wherein R² is an alkyl or alkyl benzyl group having from about 8 toabout 18 carbon atoms in the alkyl chain, each R³ is selected from thegroup consisting of --CH₂ CH₂ --, --CH₂ CH(CH₃)--, --CH₂ CH(CH₂ OH)--,--CH₂ CH₂ CH₂ --, and mixtures thereof; each R⁴ is selected from thegroup consisting of C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, benzyl ringstructures formed by joining the two R⁴ groups, --CH₂ CHOH--CHOHCOR⁶CHOHCH₂ OH wherein R⁶ is any hexose or hexose polymer having a molecularweight less than about 1000, and hydrogen when y is not 0; R⁵ is thesame as R⁴ or is an alkyl chain wherein the total number of carbon atomsof R² plus R⁵ is not more than about 18; each y is from 0 to about 10and the sum of the y values is from 0 to about 15; and X is anycompatible anion.

Highly preferred cationic surfactants are the water-soluble quaternaryammonium compounds useful in the present composition having the formula:

    R.sub.1 R.sub.2 R.sub.3 R.sub.4 N.sup.+ X.sup.-            (i)

wherein R₁ is C₈ -C₁₆ alkyl, each of R₂, R₃ and R₄ is independently C₁-C₄ alkyl, C₁ -C₄ hydroxy alkyl, benzyl, and --(C₂ H₄₀)_(x) H where xhas a value from 2 to 5, and X is an anion. Not more than one of R₂, R₃or R₄ should be benzyl.

The preferred alkyl chain length for R₁ is C₁₂ -C₁₅ particularly wherethe alkyl group is a mixture of chain lengths derived from coconut orpalm kernel fat or is derived synthetically by olefin build up or OXOalcohols synthesis. Preferred groups for R₂ R₃ and R₄ are methyl andhydroxyethyl groups and the anion X may be selected from halide,methosulphate, acetate and phosphate ions.

Examples of suitable quaternary ammonium compounds of formulae (i) foruse herein are:

coconut trimethyl ammonium chloride or bromide;

coconut methyl dihydroxyethyl ammonium chloride or bromide;

decyl triethyl ammonium chloride;

decyl dimethyl hydroxyethyl ammonium chloride or bromide;

C₁₂₋₁₅ dimethyl hydroxyethyl ammonium chloride or bromide;

coconut dimethyl hydroxyethyl ammonium chloride or bromide;

myristyl trimethyl ammonium methyl sulphate;

lauryl dimethyl benzyl ammonium chloride or bromide;

lauryl dimethyl (ethenoxy)₄ ammonium chloride or bromide;

choline esters (compounds of formula (i) wherein R₁ is --CH₂--O--C--C₁₂₋₁₄ alkyl and R₂ R₃ R₄ are methyl).

O di-alkyl imidazolines compounds of formula (i)!.

Other cationic surfactants useful herein are also described in U.S. Pat.No. 4,228,044, Cambre, issued Oct. 14, 1980.

When included therein, the laundry detergent compositions of the presentinvention typically comprise from 0% to about 25%, preferably from about3% to about 15% by weight of such cationic surfactants.

Ampholytic surfactants are also suitable for use in the laundrydetergent compositions of the present invention. These surfactants canbe broadly described as aliphatic derivatives of secondary or tertiaryamines, or aliphatic derivatives of heterocyclic secondary and tertiaryamines in which the aliphatic radical can be straight- orbranched-chain. One of the aliphatic substituents contains at leastabout 8 carbon atoms, typically from about 8 to about 18 carbon atoms,and at least one contains an anionic water-solubilizing group, e.g.carboxy, sulfonate, sulfate. See U.S. Pat. No. 3,929,678 to Laughlin etal., issued Dec. 30, 1975 at column 19, lines 18-35, for examples ofampholytic surfactants.

When included therein, the laundry detergent compositions of the presentinvention typically comprise from 0% to about 15%, preferably from about1% to about 10% by weight of such ampholytic surfactants.

Zwitterionic surfactants are also suitable for use in laundry detergentcompositions. These surfactants can be broadly described as derivativesof secondary and tertiary amines, derivatives of heterocyclic secondaryand tertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 throughcolumn 22, line 48, for examples of zwitterionic surfactants.

When included therein, the laundry detergent compositions of the presentinvention typically comprise from 0% to about 15%, preferably from about1% to about 10% by weight of such zwitterionic surfactants.

Semi-polar nonionic surfactants are a special category of nonionicsurfactants which include water-soluble amine oxides containing onealkyl moiety of from about 10 to about 18 carbon atoms and 2 moietiesselected from the group consisting of alkyl groups and hydroxyalkylgroups containing from about 1 to about 3 carbon atoms; water-solublephosphine oxides containing one alkyl moiety of from about 10 to about18 carbon atoms and 2 moieties selected from the group consisting ofalkyl groups and hydroxyalkyl groups containing from about 1 to about 3carbon atoms; and water-soluble sulfoxides containing one alkyl moietyof from about 10 to about 18 carbon atoms and a moiety selected from thegroup consisting of alkyl and hydroxyalkyl moieties of from about 1 toabout 3 carbon atoms.

Semi-polar nonionic detergent surfactants include the amine oxidesurfactants having the formula ##STR3## wherein R³ is an alkyl,hydroxyalkyl, or alkyl phenyl group or mixtures therof containing fromabout 8 to about 22 carbon atoms; R⁴ is an alkylene or hydroxyalkylenegroup containing from about 2 to about 3 carbon atoms or mixturesthereof; x is from 0 to about 3; and each R⁵ is an alkyl or hydroxyalkylgroup containing from about 1 to about 3 carbon atoms or a polyethyleneoxide group containing from about 1 to about 3 ethylene oxide groups.The R⁵ groups can be attached to each other, e.g., through an oxygen ornitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include C₁₀ -C₁₈ alkyldimethyl amine oxides and C₈ -C₁₂ alkoxy ethyl dihydroxy ethyl amineoxides.

When included therein, the laundry detergent compositions of the presentinvention typically comprise from 0% to about 15%, preferably from about1% to about 10% by weight of such semi-polar nonionic surfactants.

The present invention further provides laundry detergent compositionscomprising at least 1% by weight, preferably from about 3% to about 65%,more preferably from about 10% to about 25% by weight of totalsurfactants.

Preferred detergent ingredients that can be included are detersiveenzymes which can be included in the detergent formulations for a widevariety of purposes including removal of protein-based,carbohydrate-based, or triglyceride-based stains, for example, andprevention of refugee dye transfer. The enzymes to be incorporatedinclude proteases, amylases, lipases, cellulases, and peroxidases, aswell as mixtures thereof. Other types of enzymes may also be included.They may be of any suitable origin, such as vegetable, animal,bacterial, fungal and yeast origin.

Enzymes are normally incorporated at levels sufficient to provide up toabout 5 mg by weight, more typically about 0.05 mg to about 3 mg, ofactive enzyme per gram of the composition. Highly preferred enzymes tobe incorporated in the detergent compositions according to the presentinvention are cellulases or peroxidases and mixtures thereof.

The cellulases usable in the present invention include both bacterial orfungal cellulase. Preferably, they will have a pH optimum of between 5and 9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307,Barbesgoard et al, which discloses fungal cellulase produced fromHumicola insolens. Suitable cellulases are also disclosed inGB-A-2.075.028 ; GB-A-2.095.275 and DE-OS-2.247.832.

Examples of such cellulases are cellulases produced by a strain ofHumicola insolens (Humicola grisea var. thermoidea), particularly theHumicola strain DSM 1800, and cellulases produced by a fungus ofBacillus N or a cellulase 212-producing fungus belonging to the genusAeromonas, and cellulase extracted from the hepatopancreas of a marinemollusc (Dolabella Auricula Solander).

Other suitable cellulases are cellulases originated from HumicolaInsulens having a molecular weight of about 50 KDa, an isoelectric pointof 5.5 and containing 415 amino acids. Such cellulase are described inCopending European patent application No. 93200811.3, filed Mar. 19,1993. Especially suitable cellulase are the cellulase having color carebenefits. Examples of such cellulases are cellulase described inEuropean patent application No. 91202879.2, filed Nov. 6, 1991 Carezyme(Novo). It has been found that the N-vinyl imidazole N-vinylpyrrolidonecopolymers synergistically improve the performance in of the cellulasesin terms of colour appearance.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipasesinclude those which show a positive immunoligical cross-reaction withthe antibody of the lipase, produced by the microorganism Pseudomonasfluorescent IAM 1057. This lipase is available from Amano PharmaceuticalCo. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,"hereinafter referred to as "Amano-P".

Especially suitable Lipase are lipase such as M1 Lipase (Ibis) andLipolase (Novo).

Peroxidase enzymes are used in combination with oxygen sources, e.g.percarbonate, perborate, persulfate, hydrogen peroxide, etc. They areused for "solution bleaching", i.e. to prevent transfer of dyes ofpigments removed from substrates during wash operations to othersubstrates in the wash solution. Peroxidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in PCT Internation Application WO 89/099813 and in European Patentapplication EP No. 91202882.6, filed on Nov. 6, 1991.

It has been found that the N-vinyl imidazole N-vinylpyrrolidonecopolymers synergistically improve the dye transfer inhibitingperformance of the peroxidase.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniformis. Proteolyticenzymes suitable for removing protein-based stains that are commerciallyavailable include those sold under the tradenames Alcalase, Savinase andEsperase by Novo Industries A/S (Denmark) and Maxatase by InternationalBio-Synthetics, Inc. (The Netherlands) and FN-base by Genencor, Optimaseand opticlean by MKC.

Of interest in the category of proteolytic enzymes, especially forliquid detergent compositions, are enzymes referred to herein asProtease A and Protease B. Protease A is described in European PatentApplication 130,756. Protease B is described in European PatentApplication Serial No. 87303761.8.

Amylases include, for example, -amylases obtained from a special strainof B. licheniforms, described in more detail in British PatentSpecification No. 1,296,839 (Novo). Amylolytic proteins include, forexample, Rapidase, Maxamyl (International Bio-Synthetics, Inc.) andTermamyl,(Novo Industries).

In liquid formulations, an enzyme stabilization system is preferablyutilized. Enzyme stabilization techniques for aqueous detergentcompositions are well known in the art. For example, one technique forenzyme stabilization in aqueous solutions involves the use of freecalcium ions from sources such as calcium acetate, calcium formate andcalcium propionate. Calcium ions can be used in combination with shortchain carboxylic acid salts, preferably formates. See, for example, U.S.Pat. No. 4,318,818. It has also been proposed to use polyols likeglycerol and sorbitol. Alkoxy-alcohols, dialkylglycoethers, mixtures ofpolyvalent alcohols with polyfunctional aliphatic amines (e.g., such asdiethanolamine, triethanolamine, di-isopropanolamime, etc.), and boricacid or alkali metal borate. Enzyme stabilization techniques areadditionally disclosed and exemplified in U.S. Pat. No. 4,261,868, U.S.Pat. No. 3,600,319, and European Patent Application Publication No. 0199 405, Application No. 86200586.5. Non-boric .acid and boratestabilizers are preferred. Enzyme stabilization systems are alsodescribed, for example, in U.S. Pat. Nos. 4,261,868, 3,600,319 and3,519,570. Other suitable detergent ingredients that can be added areenzyme oxidation scavengers which are described in Copending EuropeanPatent aplication N 92870018.6 filed on Jan. 31, 1992. Examples of suchenzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

Especially preferred detergent ingredients are combinations withtechnologies which also provide a type of color care benefit. Examplesof these technologies are polyvinylpyrrolidone polymers such asdescribed in EP 0 508 034 and polyamine-N-oxide containing polymers suchas described in Copending European patent application N 92202168.8 and N93201198.4. Other examples are cellulase and/or peroxidases and/ormetallo catalysts for color maintance rejuvenation. Such metallocatalysts are described in copending European Patent Application No.92870181.2.

In addition, it has been found that the N-imidazole N-vinylpyrrolidonecopolymers according to the present invention eliminate or reduce thedeposition of the metallo-catalyst onto the fabrics resulting inimproved whiteness benefit.

Preferred detergent ingredients that can be included in the detergentcompositions of the present invention include bleaching agents.

These bleaching agent components can include one or more oxygenbleaching agents and, depending upon the bleaching agent chosen, one ormore bleach activators. When present bleaching compounds will typicallybe present at levels of from about 1% to about 10%, of the detergentcomposition. In general, bleaching compounds are optional components innon-liquid formulations, e.g. granular detergents. If present, theamount of bleach activators will typically be from about 0.1% to about60%, more typically from about 0.5% to about 40% of the bleachingcomposition.

The bleaching agent component for use herein can be any of the bleachingagents useful for detergent compositions including oxygen bleaches aswell as others known in the art.

In a method aspect, this invention further provides a method forcleaning fabrics, fibers, textiles, at temperatures below about 50° C.,especially below about 40° C., with a detergent composition containingN-vinylimidazole N-vinylpyrrolidone copolymers in combination withbleaching agents.

The bleaching agent suitable for the present invention can be anactivated or non-activated bleaching agent.

One category of oxygen bleaching agent that can be used encompassespercarboxylic acid bleaching agents and salts thereof. Suitable examplesof this class of agents include magnesium monoperoxyphthalatehexahydrate, the magnesium salt of meta-chloro perbenzoic acid,4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, U.S.patent application Ser. No. 740,446, European Patent Application0,133,354 and U.S. Pat. No. 4,412,934. Highly preferred bleaching agentsalso include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S.Pat. No. 4,634,551.

Another category of bleaching agents that can be used encompasses thehalogen bleaching agents. Examples of hypohalite bleaching agents, forexample, include trichloro isocyanuric acid and the sodium and potassiumdichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides.Such materials are normally added at 0.5-10% by weight of the finishedproduct, preferably 1-5% by weight.

Preferably, the bleaches suitable for the present invention includeperoxygen bleaches. Examples of suitable water-soluble solid peroxygenbleaches include hydrogen peroxide releasing agents such as hydrogenperoxide, perborates, e.g. perborate monohydrate, perboratetetrahydrate, persulfates, percarbonates, peroxydisulfates,perphosphates and peroxyhydrates. Preferred bleaches are percarbonatesand perborates.

The hydrogen peroxide releasing agents can be used in combination withbleach activators such as tetraacetylethylenediamine (TAED),nonanoyloxybenzenesulfonate (NOBS, described in U.S. Pat. No.4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, describedin EP 120,591) or pentaacetylglucose (PAG), which are perhydrolyzed toform a peracid as the active bleaching species, leading to improvedbleaching effect. Also suitable activators are acylated citrate esterssuch as disclosed in Copending European Patent Application No.91870207.7.

The hydrogen peroxide may also be present by adding an enzymatic system(i.e. an enzyme and a substrate therefore) which is capable ofgenerating hydrogen peroxide at the beginning or during the washingand/or rinsing process. Such enzymatic systems are disclosed in EPPatent Application 91202655.6 filed Oct. 9, 1991.

Other peroxygen bleaches suitable for the present invention includeorganic peroxyacids such as percarboxylic acids.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein. One type of non-oxygen bleachingagent of particular interest includes photoactivated bleaching agentssuch as the sulfonated zinc and/or aluminum phthalocyanines. Thesematerials can be deposited upon the substrate during the washingprocess. Upon irradiation with light, in the presence of oxygen, such asby hanging clothes out to dry in the daylight, the sulfonated zincphthalocyanine is activated and, consequently, the substrate isbleached. Preferred zinc phthalocyanine and a photoactivated bleachingprocess are described in U.S. Pat. No. 4,033,718. Typically, detergentcompositions will contain about 0.025% to about 1.25%, by weight, ofsulfonated zinc phthalocyanine.

Preferably, the compositions according to the present invention comprisea clay. It has been found that the N-vinylimidazole N-vinylpyrrolidonecopolymers according to the present invention are very compatible withthe clays in that the dye transfer inhibiting properties of the polymersare not adversely affected by the presence of clays formulatedtherewith. In addition, it has been found that the softening performanceof clays formulated with the N-vinylimidazole N-vinylpyrrolidonecopolymers has been maintained. Especially suitable are clays such asfabric softening clays which are described in EP 0 522 206.

The compositions according to the present invention may further comprisea builder system. Any conventional builder system is suitable for useherein including aluminosilicate materials, silicates, polycarboxylatesand fatty acids, materials such as ethylenediamine tetraacetate, metalion sequestrants such as aminopolyphosphonates, particularlyethylenediamine tetramethylene phosphonic acid and diethylene triaminepentamethylenephosphonic acid. Though less preferred for obviousenvironmental reasons, phosphate builders can also be used herein.

Suitable builders can be an inorganic ion exchange material, commonly aninorganic hydrated aluminosilicate material, more particularly ahydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.

Another suitable inorganic builder material is layered silicate, e.g.SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting ofsodium silicate (Na₂ Si₂ O₅).

Suitable polycarboxylates containing one carboxy group include lacticacid, glycolic acid and ether derivatives thereof as disclosed inBelgian Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylatescontaining two carboxy groups include the water-soluble salts ofsuccinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid,diglycollic acid, tartaric acid, tartronic acid and fumaric acid, aswell as the ether carboxylates described in German Offenlegenschrift2,446,686, and 2,446,687 and U.S. Pat. No. 3,935,257 and the sulfinylcarboxylates described in Belgian Patent No. 840,623. Polycarboxylatescontaining three carboxy groups include, in particular, water-solublecitrates, aconitrates and citraconates as well as succinate derivativessuch as the carboxymethyloxysuccinates described in British Patent No.1,379,241, lactoxysuccinates described in Netherlands Application7205873, and the oxypolycarboxylate materials such as2-oxa-1,1,3-propane tricarboxylates described in British Patent No.1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituentsinclude the sulfosuccinate derivatives disclosed in British Patent Nos.1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and thesulfonated pyrolysed citrates described in British Patent No. 1,082,179,while polycarboxylates containing phosphone substituents are disclosedin British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates includecyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienidepentacarboxylates,2,3,4,5-tetrahydrofuran-cis,cis,cis-tetracarboxylates,2,5-tetrahydrofuran-cis-dicarboxylates,2,2,5,5-tetrahydrofuran-tetracarboxylates,1,2,3,4,5,6-hexanehexacarboxylates and and carboxymethyl derivatives ofpolyhydric alcohols such as sorbitol, mannitol and xylitol. Aromaticpolycarboxylates include mellitic acid, pyromellitic acid and thephtalic acid derivatives disclosed in British Patent No. 1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylatescontaining up to three carboxy groups per molecule, more particularlycitrates.

Preferred builder systems for use in the present compositions include amixture of a water-insoluble aluminosilicate builder such as zeolite Aor of a layered silicate (sks/6), and a water-soluble carboxylatechelating agent such as citric acid.

A suitable chelant for inclusion in the detergent compositions inaccordance with the invention is ethylenediamine-N,N'-disuccinic acid(EDDS) or the alkali metal, alkaline earth metal, ammonium, orsubstituted ammonium salts thereof, or mixtures thereof. Preferred EDDScompounds are the free acid form and the sodium or magnesium saltthereof. Examples of such preferred sodium salts of EDDS include Na₂EDDS and Na₄ EDDS. Examples of such preferred magnesium salts of EDDSinclude MgEDDS and Mg₂ EDDS. The magnesium salts are the most preferredfor inclusion in compositions in accordance with the invention.

Especially for the liquid execution herein, suitable fatty acid buildersfor use herein are saturated or unsaturated C10-18 fatty acids, as wellas the corresponding soaps. Preferred saturated species have from 12 to16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acidis oleic acid.

Preferred builder systems for use in granular compositions include amixture of a water-insoluble aluminosilicate builder such as zeolite A,and a watersoluble carboxylate chelating agent such as citric acid.

Other builder materials that can form part of the builder system for usein granular compositions include inorganic materials such as alkalimetal carbonates, bicarbonates, silicates, and organic materials such asthe organic phosphonates, amino polyalkylene phosphonates and aminopolycarboxylates.

Other suitable water-soluble organic salts are the homo- or co-polymericacids or their salts, in which the polycarboxylic acid comprises atleast two carboxyl radicals separated from each other by not more thantwo carbon atoms.

Polymers of this type are disclosed in GB-A-1,596,756. Examples of suchsalts are polyacrylates of MW 2000-5000 and their copolymers with maleicanhydride, such copolymers having a molecular weight of from 20,000 to70,000, especially about 40,000.

Detergency builder salts are normally included in amounts of from 10% to80% by weight of the composition preferably from 20% to 70% and mostusually from 30% to 60% by weight.

Another optional ingredient is a suds suppressor, exemplified bysilicones, and silica-silicone mixtures. Silicones can be generallyrepresented by alkylated polysiloxane materials while silica is normallyused in finely divided forms exemplified by silica aerogels and xerogelsand hydrophobic silicas of various types. These materials can beincorporated as particulates in which the suds suppressor isadvantageously releasably incorporated in a water-soluble orwater-dispersible, substantially non-surface-active detergentimpermeable carrier. Alternatively the suds suppressor can be dissolvedor dispersed in a liquid carrier and applied by spraying on to one ormore of the other components.

A preferred silicone suds controlling agent is disclosed in Bartollotaet al. U.S. Pat. No. 3,933,672. Other particularly useful sudssuppressors are the self-emulsifying silicone suds suppressors,described in German Patent Application DTOS 2 646 126 published Apr. 28,1977. An example of such a compound is DC-544, commercially availablefrom Dow Corning, which is a siloxane-glycol copolymer. Especiallypreferred suds controlling agent are the suds suppressor systemcomprising a mixture of silicone oils and 2-alkyl-alcanols. Suitable2-alkyl-alcanols are 2-butyl-octanol which are commercially availableunder the trade name Isofol 12 R.

Such suds suppressor system are described in Copending European Patentapplication N 92870174.7 filed 10 Nov. 1992.

Especially preferred silicone suds controlling agents are described inCopending European Patent application N.92201649.8 Said compositions cancomprise a silicone/silica mixture in combination with fumed nonporoussilica such as Aerosil®.

The suds suppressors described above are normally employed at levels offrom 0.001% to 2% by weight of the composition, preferably from 0.01% to1% by weight.

Other components used in detergent compositions may be employed, such assoil-suspending agents soil-release agents, optical brighteners,abrasives, bactericides, tarnish inhibitors, coloring agents, and/orencapsulated or non-encapsulated perfumes.

Antiredeposition and soil suspension agents suitable herein includecellulose derivatives such as methylcellulose, carboxymethylcelluloseand hydroxyethylcellulose, and homo- or co-polymeric polycarboxylicacids or their salts. Polymers of this type include the polyacrylatesand maleic anhydride-acrylic acid copolymers previously mentioned asbuilders, as well as copolymers of maleic anhydride with ethylene,methylvinyl ether or methacrylic acid, the maleic anhydride constitutingat least 20 mole percent of the copolymer. These materials are normallyused at levels of from 0.5% to 10% by weight, more preferably from 0.75%to 8%, most preferably from 1% to 6% by weight of the composition.

Preferred optical brighteners are anionic in character, examples ofwhich are disodium 4,4¹-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2:2¹disulphonate, disodium 4,-4¹-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:2¹-disulphonate, disodium 4,4¹ -bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2¹ -disulphonate,monosodium 4¹,4¹¹-bis-(2,4-dianilino-s-triazin-6ylamino)stilbene-2-sulphonate, disodium4,4¹-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2¹ -disulphonate, disodium 4,4¹-bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2¹ disulphonate, disodium4,4¹bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2¹disulphonate and sodium 2(stilbyl-4¹¹ -(naphtho-1¹,2¹:4,5)-1,2,3-triazole-2¹¹ -sulphonate.

Other useful polymeric materials are the polyethylene glycols,particularly those of molecular weight 1000-10000, more particularly2000 to 8000 and most preferably about 4000. These are used at levels offrom 0.20% to 5% more preferably from 0.25% to 2.5% by weight. Thesepolymers and the previously mentioned homo- or co-polymericpolycarboxylate salts are valuable for improving whiteness maintenance,fabric ash deposition, and cleaning performance on clay, proteinaceousand oxidizable soils in the presence of transition metal impurities.

Soil release agents useful in compositions of the present invention areconventionally copolymers or terpolymers of terephthalic acid withethylene glycol and/or propylene glycol units in various arrangements.Examples of such polymers are disclosed in the commonly assigned U.S.Pat. Nos. 4,116,885 and 4,711,730 and European Published PatentApplication No. 0 272 033. A particular preferred polymer in accordancewith EP-A-0 272 033 has the formula

    (CH.sub.3 (PEG).sub.43).sub.0.75 (POH).sub.0.25  T-PO).sub.2.8 (T-PEG).sub.0.4 !T(POH).sub.0.25 (PEG).sub.43 CH.sub.3).sub.0.75

where PEG is --(OC₂ H₄)O--, PO is (OC₃ H₆ O) and T is (pcOC₆ H₄ CO).

Also very useful are modified polyesters as random copolymers ofdimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and1-2 propane diol, the end groups consisting primarily of sulphobenzoateand secondarily of mono esters of ethylene glycol and/or propane-diol.The target is to obtain a polymer capped at both end by sulphobenzoategroups, "primarily", in the present context most of said copolymersherein will be end-capped by sulphobenzoate groups. However, somecopolymers will be less than fully capped, and therefore their endgroups may consist of monoester of ethylene glycol and/or propane 1-2diol, thereof consist "secondarily" of such species.

The selected polyesters herein contain about 46% by weight of dimethylterephtalic acid, about 16% by weight of propane -1.2 diol, about 10% byweight ethylene glycol about 13% by weight of dimethyl sulfobenzoid acidand about 15% by weight of sulfoisophtalic acid, and have a molecularweight of about 3,000. The polyesters and their method of preparationare described in detail in EPA 311 342.

The detergent compositions according to the invention can be in liquid,paste, gels or granular forms. Especially preferred detergentcompositions are detergent compositions having a pH between 7-11, morepreferably a pH between 9-10.5.

Granular compositions according to the present invention can also be in"compact form", i.e. they may have a relatively higher density thanconventional granular detergents, i.e. from 550 to 950 g/l; in suchcase, the granular detergent compositions according to the presentinvention will contain a lower amount of "inorganic filler salt",compared to conventional granular detergents; typical filler salts arealkaline earth metal salts of sulphates and chlorides, typically sodiumsulphate; "compact" detergents typically comprise not more than 10%filler salt. The liquid compositions according to the present inventioncan also be in "concentrated form", in such case, the liquid detergentcompositions according to the present invention will contain a loweramount of water, compared to conventional liquid detergents. Typically,the water content of the concentrated liquid detergent is less than 30%,more preferably less than 20%, most preferably less than 10% by weightof the detergent compositions. Other examples of liquid compositions areanhydrous compositions containing substantially no water.

Both aqueous and non-aqueous liquid compositions can be structured ornon-structured.

The present invention also relates to a process for inhibiting dyetransfer from one fabric to another of solubilized and suspended dyesencountered during fabric laundering operations involving coloredfabrics.

The process comprises contacting fabrics with a laundering solution ashereinbefore described.

The process of the invention is conveniently carried out in the courseof the washing process. The washing process is preferably carried out at5° C. to 75° C., especially 20 to 60, but the polymers are effective atup to 95° C. and higher temperatures. The pH of the treatment solutionis preferably from 7 to 11, especially from 7.5 to 10.5.

The process and compositions of the invention can also be used asdetergent additive products. Such additive products are intended tosupplement or boost the performance of conventional detergentcompositions. The detergent compositions according to the presentinvention include compositions which are to be used for cleaningsubstrates, such as fabrics, fibers, hard surfaces, skin etc., forexample hard surface cleaning compositions (with or without abrasives),laundry detergent compositions, automatic and non automatic dishwashingcompositions.

The following examples are meant to exemplify compositions of thepresent invention, but are not necessarily meant to limit or otherwisedefine the scope of the invention, said scope being determined accordingto claims which follow.

EXAMPLE I (A/B/C/D)

A liquid detergent composition according to the present invention isprepared, having the following compositions:

    ______________________________________                                        % by weight af the total detergent composition                                                   A      B       C    D                                      ______________________________________                                        Linear alkylbenzene sulfonate                                                                    10     --      --   --                                     Polyhydroxy fatty acid amide                                                                     --     5       --   3                                      Alkyl alkoxylated sulfate                                                                        --     --      9    4                                      Alky1 sulphate     4      8       4    15                                     Fatty alcohol (C.sub.12 -C.sub.15) ethoxylate                                                    12     12      12   5                                      Fatty acid         10     10      10   10                                     Oleic acid         4      4       4    --                                     Citric acid        1      1       1    1                                      Diethylenetriaminepentamethylene                                                                 1.5    1.5     1.5  1.5                                    Phosphonic acid                                                               NaOH               3.4    3.4     3.4  3.4                                    Propanediol        1.5    1.5     1.5  1.5                                    Ethanol            10     10      10   10                                     Ethoxylated tetraethylene pentamine                                                              0.7    0.7     0.7  0.7                                    Thermamyl R 300 KNU/g                                                                            0.1    0.1     0.1  0.1                                    Carezyme R 5000 CEVU/g                                                                           0.02   0.02    0.02 0.02                                   Protease 40 mg/g   1.8    1.8     1.8  1.8                                    Lipolase R 100 KLU/g                                                                             0.1    0.1     0.1  0.1                                    Endoglucanase A 5000 CEVU/g                                                                      0.5    0.5     0.5  0.5                                    Suds supressor (ISOFOL.sup.r)                                                                    2.5    2.5     2.5  2.5                                    H.sub.2 O.sub.2    7.5    7.5     --   --                                     N-vinylimidazole N-vinyl                                                                         0.1-1  0.1-1   0.1-1                                                                              0.1-1                                  pyrrolidone copolymer                                                         Minors             up to 100                                                  ______________________________________                                    

EXAMPLE II (A/B/C/D)

A liquid detergent composition according to the present invention isprepared, having the following compositions:

    ______________________________________                                        % by weight of the total detergent composition                                                   A      B       C    D                                      ______________________________________                                        Linear alkylbenzene sulfonate                                                                    10     --      --   --                                     Polyhydroxy fatty acid amide                                                                     --     5       --   3                                      Alkyl alkoxylated sulfate                                                                        --     --      9    4                                      Alkyl sulphate     4      8       4    15                                     Fatty alcohol (C.sub.12 -C.sub.15) ethoxylate                                                    12     12      12   5                                      Fatty acid         10     10      10   10                                     Oleic acid         4      4       4    --                                     Citric acid        1      1       1    1                                      Diethylenetriaminepentamethylene                                                                 1.5    1.5     1.5  1.5                                    Phosphonic acid                                                               NaOH               3.4    3.4     3.4  3.4                                    Propanediol        1.5    1.5     1.5  1.5                                    Ethanol            10     10      10   10                                     Ethoxylated tetraethylene pentamine                                                              0.7    0.7     0.7  0.7                                    Thermamyl R 300 KNU/g                                                                            0.1    0.1     0.1  0.1                                    Carezyme R 5000 CEVU/g                                                                           0.02   0.02    0.02 0.02                                   Protease 40 mg/g   1.8    1.8     1.8  1.8                                    Lipolase R 100 KLU/g                                                                             0.1    0.1     0.1  0.1                                    Endoglucanase A 5000 CEVU/g                                                                      0.5    0.5     0.5  0.5                                    Suds supressor (ISOFOL.sup.r)                                                                    2.5    2.5     2.5  2.5                                    H.sub.2 O.sub.2    7.5    7.5     --   --                                     N-vinylimidazole N-vinylpyrrolidone                                                              0.1-1  0.1-1   0.1-1                                                                              0.1-1                                  copolymer                                                                     Metallo catalyst   0.1-1  0.1-1   0.1-1                                                                              0.1-1                                  Poly(4-vinylpyridine)-N-oxide                                                                    0.1-1  0.1-1   0.1-1                                                                              0.1-1                                  clay               --     --      4    4                                      peroxidase         0.1    0.1     --   --                                     Minors             up to 100                                                  ______________________________________                                    

EXAMPLE III (A/B/C/D/E)

A compact granular detergent composition according to the presentinvention is prepared, having the following formulation:

    ______________________________________                                        % by weight of the total detergent composition                                                 A      B      C    D     E                                   ______________________________________                                        Linear alkyl benzene sulphonat                                                                 11.40  --     --   --    --                                  Polyhydroxy fatty acid amide                                                                   --     10     --   --    --                                  Alkyl alkoxylated sulfate                                                                      --     --     9    9     9                                   Tallow alkyl sulphate                                                                          1.80   1.80   1.80 1.80  1.80                                C.sub.45  alkyl sulphate                                                                       3.00   3.00   3.00 3.00  3.00                                C.sub.45  alcohol 7 times ethoxylate                                                           4.00   4.00   4.00 4.00  4.00                                Tallow alcohol 11 times                                                                        1.80   1.80   1.80 1.80  1.80                                ethoxylated                                                                   Dispersant       0.07   0.07   0.07 0.07  0.07                                Silicone fluid   0.80   0.80   0.80 0.80  0.80                                Trisodium citrate                                                                              14.00  14.00  14.00                                                                              14.00 14.00                               Citric acid      3.00   3.00   3.00 3.00  3.00                                Zeolite          32.50  32.50  32.50                                                                              32.50 32.50                               Diethylenetriamine pentanethy-                                                                 0.6    0.6    0.6  0.6   0.6                                 lene phosphonic acid                                                          Maleic acid acrylic acid                                                                       5.00   5.00   5.00 5.00  5.00                                copolymer                                                                     Cellulase (active protein)                                                                     0.03   0.03   0.03 0.03  0.03                                Alkalase/BAN     0.60   0.60   0.60 0.60  0.60                                Lipolase         0.36   0.36   0.36 0.36  0.36                                Sodium silicate  2.00   2.00   2.00 2.00  2.00                                Sodium sulphate  3.50   3.50   3.50 3.50  3.50                                Percarbonate     --     --     --   20    --                                  Perborate        15     15     15   --    --                                  TAED             5      --     5    5     --                                  N-vinylimidazole N-vinyl-                                                                      0.1-1  0.1-1  0.1-1                                                                              0.1-1 0.1-1                               pyrrolidone copolymer                                                         Minors           up to 100                                                    ______________________________________                                    

EXAMPLE IV (A/B/C/D/E)

A compact granular detergent composition according to the presentinvention is prepared, having the following formulation:

    ______________________________________                                        % by weight of the total detergent composition                                                 A      B      C    D     E                                   ______________________________________                                        Linear alkyl benzene sulphonat                                                                 11.40  --     --   --    --                                  Polyhydroxy fatty acid amide                                                                   --     10     --   --    --                                  Alkyl alkoxylated sulfate                                                                      --     --     9    9     9                                   Tallow alkyl sulphate                                                                          1.80   1.80   1.80 1.80  1.80                                C.sub.45  alkyl sulphate                                                                       3.00   3.00   3.00 3.00  3.00                                C.sub.45  alcohol 7 times ethoxylate                                                           4.00   4.00   4.00 4.00  4.00                                Tallow alcohol 11 times                                                                        1.80   1.80   1.80 1.80  1.80                                ethoxylated                                                                   Dispersant       0.07   0.07   0.07 0.07  0.07                                Silicone fluid   0.80   0.80   0.80 0.80  0.80                                Trisodium citrate                                                                              14.00  14.00  14.00                                                                              14.00 14.00                               Citric acid      3.00   3.00   3.00 3.00  3.00                                Zeolite          32.50  32.50  32.50                                                                              32.50 32.50                               Diethylenetriamine pentanethy-                                                                 0.6    0.6    0.6  0.6   0.6                                 lene phosphonic acid                                                          Maleic acid acrylic acid                                                                       5.00   5.00   5.00 5.00  5.00                                copolymer                                                                     Cellulase (active protein)                                                                     0.03   0.03   0.03 0.03  0.03                                Savinase         0.60   0.60   0.60 0.60  0.60                                Lipolase         0.36   0.36   0.36 0.36  0.36                                Sodium silicate  2.00   2.00   2.00 2.00  2.00                                Sodium sulphate  3.50   3.50   3.50 3.50  3.50                                Percarbonate     --     --     --   20    --                                  Perborate        15     15     15   --    --                                  TAED             5      --     5    5     --                                  N-vinylimidazole N-vinyl-                                                                      0.1-1  0.1-1  0.1-1                                                                              0.1-1 0.1-1                               pyrrolidone copolymer                                                         Metallo catalyst 0.1-1  0.1-1  0.1-1                                                                              0.1-1 0.1-1                               Poly(4-vinylpyridine)-N-oxide                                                                  0.1-1  0.1-1  0.1-1                                                                              0.1-1 0.1-1                               Clay             --     --     --   4     4                                   peroxidase       --     0.1    0.1  --    --                                  Minors           up to 100                                                    ______________________________________                                    

The above compositions (Example I, II (A/B/C/D) and II ,IV (A/B/C/D/E))were very good at displaying excellent cleaning and detergencyperformance with outstanding color-care performance on colored fabricsand mixed loads of colored and white fabrics.

We claim:
 1. A detergent composition comprising:clay; a metallocatalyst; greater than 1% by weight of the detergent composition of asurfactant system; and from 0.01% to 10% by weight of the detergentcomposition of a copolymer of N-vinylimidazole and N-vinylpyrrolidone,the copolymer having a molar ratio of N-vinylimidazole toN-vinylpyrrolidone of from 1:1 to 1:0.2 and an average molecular weightof from 5,000 to 50,000.
 2. The detergent composition according to claim1, wherein the copolymer has an average molecular weight of from 8,000to 30,000.
 3. The detergent composition according to claim 1, whereinthe copolymer has an average molecular weight of from 10,000 to 20,000.4. The detergent composition according to claim 1, wherein the molarratio of N-vinylimidazole to N-vinylpyrrolidone is in the range of from1:0.8 to 1:0.3.
 5. The detergent composition according to claim 1,wherein the molar ratio of N-vinylimidazole to N-vinylpyrrolidone is inthe range of from 1:0.6 to 1:0.4.
 6. The detergent composition accordingto claim 1, comprising from 0.05 to 5.0% by weight of the copolymer. 7.The detergent composition according to claim 1, comprising from 0.1 to1.0% by weight of the copolymer.
 8. The detergent composition accordingto claim 1, wherein the detergent composition comprises 3 to 65% byweight of the surfactant system.
 9. The detergent composition accordingto claim 1, wherein the detergent composition comprises 10 to 25% byweight of the surfactant system.
 10. The detergent composition accordingto claim 1, wherein the surfactant system comprises anionic surfactantsin an amount of 1 to 40% by weight of the detergent composition.
 11. Thedetergent composition according to claim 1, wherein the detergentcomposition has a pH between 7 and
 11. 12. The detergent compositionaccording to claim 1, wherein the detergent composition has a pH between9 and 10.5.
 13. The detergent composition according to claim 1, whereinthe detergent composition is granular.
 14. The detergent compositionaccording to claim 1, further comprising an enzyme selected from thegroup consisting of cellulases, peroxidases and mixtures thereof.
 15. Adetergent composition comprising clay, greater than 1% by weight of thedetergent composition of a surfactant system, and from 0.01% to 10% byweight of the detergent composition of a copolymer of N-vinylimidazoleand N-vinylpyrrolidone, the copolymer having a molar ratio ofN-vinylimidazole to N-vinylpyzrrolidone of from 1:0.8 to 1:0.3 and anaverage molecular weight of from 10,000 to 20,000.